Haloaryl aziridinecarboxamides



g 2,775,58i I HALOARYL AZIRIDINECARBQXAMIDES Bryant C.;Fischback,;Walnut creleana; Guy. H. Harris,

Concord, Califl, assignors to The Dow ChemicalCompany, Midland, Mich, a corporation v of ll elaware NoDrawing. Application May 23, 1955; i Serial No. 510,564

6 Claims. (Cl. 2604-239) 'The' present invention is concerned with novel haloarylaziridine carboxamides of the formula H2 NH (J-N l GHY In this and succeeding formulae, one of the X symbols represents chlorine, bromine or iodine and the remaining X symbols each represent hydrogen, methyl, chlorine,

bromine or iodine, Z represents oxygen or sulfur and represents hydrogen or a lowe alkyl radical. The expre'ssion lower alkylis inclusive of alkyl radicals containing from lto 4 carbon atoms, inclusive. The new compounds are crystalline solid materials which aresomewhat soluble in many organic solvents and of very iow solubility in pentane and water.

The compounds are valuable as parasiticidesand adapted to be employedas active toxicconstituents of: dis infectant and germicide compositions for the control of 30 The new compoundsmay be prepared by mixing or many common bacterial and fungal organisms.

blending aziridine or a 2-lowe r alkylaz iridin e with a haloaryl isocyanate or isothiocyanat e of the formula X The contacting-of the reagents conveniently may be carried out in'an ine'rt organic solvent such as diethyl'ether,

diisopropyl ether; benzene, toluene or an aliphatichydifo carbon such as pentanei The amount of'the'aziridiiieandf .by cooling and diluting the reaction mixture with a' suit-- able solvent such as pentane. i The precipitated product may be separated by filtration and thereafter purified'by washing with pentane or ether ahd recrystallizing from an organic solvent such as benzene. i t

In carrying out the reaction, the aziridine'or-"2-lower atlkyl aziridine and cyanate reagent may be contacted-portionwise in the inert solvent. This operationis'c'arried out with stirring and at a'temperature offrorn 10 toSO" C. It is preferable tocool the solutionsofreactan-ts to about 5 C. before contacting. Following the contacting of the reagents,"stirring iscontinued for" a short period of time to complete tliereactibii.' The' ractioii mixture is then treated as previously described to separate the desiredproduct. I q,

The following ex'a p'l'es "illusttatetlieinvention but are not tobconstrued as limiting:

\ Uflitsd S ews Pm Q I ture as a crystalline solid. The latter liters of diethyl ether.

t r 2,775,587 I Pitented Dec; 25, 1 956 :addition'was carried out over a p 'eriddof 10 riiirn ates at a temperature of from 20 to 35 C. Following the addition, stirring was continiidifor' 0.5 hour 6 complete the reaction. During the reaction, a 4 chloro l-a zir idinethiocarboxanilide product precipitatedinthe reac tiori mixwas separated by filtration, washed with diethyl ether and dried. The dried product melted at 108 C. with decomposition and weighed 39.3 grams. The productliad nitrogen, sulfur and chlorine contents'of 12.57, 14.5 and 16,13 erceive spectively. Theoretical it ens] correspond to 13.18, 15.08 and 16.68 percent, respectively.

Example 2.3-chl0r0-1-aziridinecarb0xanilide (0.813 mole) of 3-chlorophenyl isocyanate dispersed in 600 milliliters of n-pentane. The addition was carried out over a period of one-third hour and ate. temperature of from 15 to 35 C. Following the additiomstirring" was continued for 0.5 hour to complete the reaction. The

reaction mixture was then filtered'to separate ai3-ch.lorol-aziridinecarboxanilide product as a crystalline residue. The latter was washed with n-pentane and recrystallized frombenzene. The recrystallized product weighed 149.5 grams and had a melting point of 93.8 -95.2f C., a nine: gen content of 14.1 percent and a chlorine content of 17.7 percent, Theory requires a nitrogen content'of 14.25 er: cent and a chlorine content of 18.03 percent.

Example 3.3',4-dichl0ro-1-aziridincarboxanilide 10 grams (0.232 mole) of aziridine was-dissolved in milliliters of diethyl ether and the 're'sulting solution' added" rapidly with stirring and cooling to 47 grams(0.25 mole) of 3,4-dichlorophenyl isocyanate dispersed @250 milli- Prior to the addition, the latter isocyanate solution had been cooled to a temperature of about 5 C. During the addition, the temperature of the reaction mixture rose rapidlyto'about 35 C. Fol lowing the addition, stirring was continued for one-half hour to assure completion of the reaction. During the reaction, a 3,4-dichloro-l-aziridinecarboxanilide protiuct.

precipitated in the mixtureas a crystalline solid. The

latter was separated by filtration, washed with' diethyl I ether and dried. The ether filtrate was also'evaporated to dryness to obtain an additional crop: of product. The

latterproduct was thereafter dissolved in acetone and the. product thereafter precipitated out of the solutio'n'byjdilutioh with an ether-pentane mixture. The two products were then combined and found to melt at"l03,5 1 04; C. and have nitrogen and chlorine contents of 11.77 aitd30.7" percent, respectively.

Example 4.4'-br0m0-1 aziridinecarboxartilide Five grams (0.116 mole) of aziridine was dissolved in: 25 milliliters of pentaneand the'resul ting' solution added portionwise with stirring and cooling"to 24.8 grams"(0.'l25 mole) of 4-bromophenyl isocyanate dispersed-in l00rnil liliters of pentane. Theaddition" was"cariiedoiifoven a period offive minutes, and 'at ateniperaturdoffromi 25 to 35 C. Following the addition, stirriti'ig wasconl- Example 5.-.4T-.chlro-1aziridinecarbbmnilide Ten grams (0.232 mole) of aziridine was dissolved in 2'5 milliliters of diethyl ether and the resulting solution added p ortio'nwi se with stirring and cooling to 35.7 grams (0.232 mole) of 4-chlorophenyl isocyanate dispersed'in 100 milliliters of diethyl ether. The addition was carried out over a period of five minutes and at a temperature of from 25 to 35 C. Following the addition, stirring was continued for 0.5 hour to insure completion of the reaction. During the reaction, a 4-chloro-1- aziridinecarboxanilide product precipitatedin the, mixture as a crystalline solid. The latter was separated by filtration, Washed with 'diethyl ether and dried and the'dried product found to have a chlorine content of 17.99 percent. Thedried product was thereafter recrystallized from benzene and found to melt at 134.8135.5 C.

Example 6.-4-iod0-2-n-butyl-1-aziridinecarb0xanilide 0.3 mole of Z-n-butyl aziridine is dissolved in 60 milliliters of diethyl ether and the resulting solution added portionwise with' stirring and cooling to 0.3 mole of 4- iodophenyl isothiocyanate dispersed in 300 milliliters of diethyl ether. The addition is carried out over a period of minutes and at a temperature of from to 35 C. Following the addition, stirring is continued for onehalf hourto complete the reaction. During the reaction, a 4-iodo-2-n-butyl-1-aziridinethiocarboxanilide product precipitates in the mixture as a crystalline solid and is separated by filtration.

Example 7.-3 -chlor0- {,'-methyl-1 -aziridinecarboxanilide 6.5 grams (0.15 mole) of aziridine was dissolved in 50 milliliters of n-pentane and the resulting solution added rapidly with stirring and cooling to 24 grams (0.143

Example 8 0.2 mole of l-methyl aziridine is dissolved in 75 milliliters of n-pentane and the resulting solution added portionwise' with stirring and cooling to 0.2 mole of 3,4,5-trichlorophenyl isothiocyanate dispersed in 250 milliliters of n-pentane'. stirred for one-half hour and thereafter cooled and filtered. As a result of these operations, there is obtained a 3,4,5- trichloroZ-methyll-aziridinethiocarboxanilide product as a crystalline solid.

In a similar manner, other haloaryl aziridinecarboxamides may be prepared as follows:

3-iodo-2-n-butyl-1-aziridinethiocarboxanilide by the reaction of Z-n-butyl aziridine with 3-iodophenyl isothiocyanate.

3',4' dibromo-Z-isopropyl-l-aziridinecarboxanilide by the reaction of 2-isopropylaziridine with 3,4-dibromophenyl isocyanate.

The reaction mixture is then 3',4'-diiodo-l-aziridinecarboxanilide by the reaction of aziridine with 3,4-diiodophenyl isocyanate.

3-bromo-4'-chloro-1-aziridinecarboxanilide by reaction of aziridine with3-bromo-4-chlorophenyl isocyanate. I

, 4-bromo-2-ethyl1-aziridinethiocarboxanilide by the reaction of 2-ethyl aziridine with 4-bromophenyl isothiocyanate.

The products of the preceding examples are effective as fungicides for the control of many common fungal organisms such as Alternaria s0lani.- In a representative operation, an aqueous dispersion of 4'-chloro-1-aziridinecarboxanilide was employed for the control of the germination of the spores of Alzernaria solani. In such operation, the degree of control was calculated as the minimum dose in parts by weight of the 4-chloro-1- aziridinecarboxanilide compound per million parts by weight of the aqueous composition sutficient to bring about a 50 percent inhibition of spore germination. The latter dosage may be referred to as the ED50 dose. 4'- chloro 1-aziridine carboxanilide had an ED-50 dose of 5 parts per million. In a further operation, poultry feed compositions containing 0.1 percent of this compound were employed for the control of turkey blackhead. In such operations, 100 percent controls of blackhead were obtained. 7

The haloaryl isothiocyanates as employed in accordance with the teachings of the present invention may be prepared by reacting together equimolecular proportions of a suitable haloaniline or halotoluidine, carbon bisulfide and an alkali metal hydroxide or ammonium hydroxide to produce an alkali metal or ammonium haloaryldithiocarbamate. The latter carbamate compound is then treated in aqueous solution with an excess of lead nitrate and the resulting mixture steam distilled to separate the haloaryl isothiocyanate.

In an alternative method, the haloaryl isothiocyanates are prepared by reacting one molecular proportion of a suitable haloaniline or halotoluidine with one molecular proportion of thiophosgene in an inert solvent? Following the reaction, the haloaryl isothiocyanate compound is separated by vacuum distillation.

The haloaryl isocyanates as employed in the present invention may be prepared by reacting one molecular portion of a suitable molten haloaniline or halotoluidine hydrochloride with one molecular proportion of phosgene. Following the reaction the desired haloaryl isocyanate product is recovered by conventional methods.

We claim:

1. A compound of the formula l CHY X wherein one of the X symbols represents at least one member of the group consisting of bromine, chlorine and 3',5-dich1oro-2-methyl-1-aziridinethiocarboxanilide by the reaction of Z-methyl aziridine with 3,5-dichloropheny iodine, and the remaining X symbols each represent a member of the group consisting of hydrogen, methyl, chlorine, bromine and iodine, Z represents a member of the group consisting of oxygen and sulfur and Y represents amember of the group consisting of hydrogen and the lower alkyl radicals.

i 4-chloro-1-aziridine carboxanilide.

. 4-bromo-1-aziridinecarboxanilide. 3',4-dichloro-1-aziridinecarboxanilide. 3-chloro-l-aziridinecarboxanilide. 4'-chloro1-aziridinethiocarboxanilide.

ave-AWN 

1. A COMPOUND OF THE FORMULA 